High and low temperature resistant allyl molding compound and preparation method thereof

Abstract

The invention discloses a high and low temperature resistant allyl molding compound and a preparation method thereof. The high and low temperature resistant allyl molding compound is prepared from the following components in parts by weight: 25-35 parts of solid modified allyl resin, 22-32 parts of reinforced fiber, 24-34 parts of filler, 5-10 parts of curing agent, 1-2 parts of release agent, 0-5 parts of flame retardant and 0-5 parts of pigment. Wherein the solid-state modified allyl resin is obtained by modifying low-molecular-weight solid-state allyl resin by using a composite modifier obtained by dissolving an alkene compound with a fluorene ring and an acrylate compound with double alicyclic rings in a solvent. According to the invention, an alkene compound with a fluorene ring and an acrylate compound with double alicyclic rings are combined according to a specific ratio to serve as a composite modifier, and the alkene compound with the fluorene ring and the acrylate compound with double alicyclic rings have a synergistic effect, so that the glass-transition temperature is effectively increased while the thermal expansion coefficient is remarkably reduced; the finally prepared allyl molding compound has excellent dimensional stability, high and low temperature resistance, impact resistance and wear resistance.

Description

Technical Field

[0001] The invention relates to a thermosetting molding compound, in particular to a high and low temperature resistant allyl molding compound and a preparation method thereof. Background Art

[0002] With the rapid development of aerospace, deep-sea navigation and other fields, the demand for high-performance electronic components is also growing. The insulating shells of electronic components (such as aviation toggle switches, etc.) that can maintain stable electrical and mechanical properties under extremely complex environmental conditions with constantly changing high and low temperatures have higher requirements on the performance of the required electrical molding compounds. During the use of ordinary electronic components, because ordinary insulating shell materials have a large thermal expansion coefficient and a low glass transition temperature, they are prone to deformation in alternating hot and cold environments, resulting in looseness between the insulating shell and the metal fasteners, posing a safety hazard. In order to improve the structural strength and reliability of such electronic components, it is necessary to provide insulating shell materials with a lower thermal expansion coefficient and a higher glass transition temperature.

[0003] At present, epoxy resin materials are mostly used as electronic plastic packaging materials. For example, the invention patent with publication number CN117801745A discloses a chip packaging material with a low thermal expansion coefficient. The three resins of trifunctional epoxy resin, polyether modified epoxy resin and naphthalene epoxy resin are cured by a curing agent to prepare an epoxy resin filling glue with a low thermal expansion coefficient. However, this type of epoxy resin material is not suitable for injection molding. Allyl molding plastic is more suitable for manufacturing microelectronic components due to its excellent electrical properties, mechanical properties, dimensional stability, heat resistance, chemical corrosion resistance, and suitability for injection molding. However, the thermal expansion coefficient of ordinary allyl molding plastic is not ideal, and the glass transition temperature is low, which causes it to deform under extremely complex environmental conditions such as constant changes in high and low temperatures, thereby failing to meet the use requirements of high-performance electronic components.

[0004] On the basis of the excellent performance of allyl molding compounds, how to reduce their thermal expansion coefficient and shrinkage rate, increase their glass transition temperature, and enable allyl molding compounds to better meet the use requirements of high-performance electronic components in special fields (such as aerospace, deep-sea diving and other harsh environments) and improve the reliability of electronic components has become a technical problem that needs to be solved urgently in this field. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a high and low temperature resistant allyl molding compound with low thermal expansion coefficient, low shrinkage rate and high glass transition temperature and a preparation method thereof.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0007] A high and low temperature resistant allyl molding compound is made of the following components in weight ratio:

[0008] Solid modified allyl resin 25-35, reinforcing fiber 22-32, filler 24-34, curing agent 5-10, release agent 1-2, flame retardant 0-5, pigment 0-5; wherein,

[0009] The solid modified allyl resin is prepared by the following method:

[0010] a) weighing 15-30% of an olefin compound having a fluorene ring, 15-30% of an acrylate compound having a double aliphatic ring and the remainder of a solvent by weight percentage; dissolving the olefin compound having a fluorene ring and the acrylate compound having a double aliphatic ring in the solvent to obtain a composite modifier; wherein,

[0011] The olefin compound having a fluorene ring is a compound represented by the following formula (A):

[0012]

[0013] In formula (A), R represents one or a combination of two or more of an alkylene group, a phenyl group, a carboxyl group, a carbonyl group and an ether group;

[0014] The acrylate compound having a double aliphatic ring is isobornyl acrylate and / or isobornyl methacrylate;

[0015] The solvent is one or a combination of two or more selected from ethanol, isopropanol, ether, toluene and xylene;

[0016] b) weighing 58-65% of a low molecular weight solid allyl resin, 30-40% of a composite modifier and the remainder of an initiator by weight percentage; placing the low molecular weight solid allyl resin in a reaction kettle, adding the composite modifier, stirring evenly, heating to 80-130° C., adding the initiator to react, cooling after the reaction is completed, and crushing to obtain a solid modified allyl resin.

[0017] The applicant discovered in the experiment that by modifying the low molecular weight solid allyl ester resin with a modifier prepared by compounding an olefin compound having a fluorene ring and an acrylate compound having a bicyclic aliphatic ring in a specific proportion, the obtained solid modified allyl resin can obtain extremely excellent dimensional stability and high and low temperature resistance. Further application of the modified allyl resin in allyl molding compounds can better meet the use requirements of high-performance electronic components in special fields.

[0018] In the above technical solution, the weight ratio of the components is preferably:

[0019] Solid modified allyl resin 28-32, reinforcing fiber 25-30, filler 28-32, curing agent 5-8, release agent 1-1.5, flame retardant 0-2, pigment 0-2.

[0020] In the above technical solution, the reinforcing fiber, filler, curing agent, release agent, flame retardant and pigment can be conventionally selected in the prior art. Preferably, they are as follows:

[0021] The reinforcing fibers are preferably inorganic fibers, and specifically may be one or a combination of two or more selected from chopped alkali-free glass fibers, basalt fibers, and needle-shaped wollastonite.

[0022] The filler is one or a combination of two or more selected from magnesium hydroxide, aluminum hydroxide, zirconium tungstate, calcium carbonate, silicon powder, quartz powder, mica powder and kaolin. When the filler contains magnesium hydroxide and / or aluminum hydroxide, the formula of the high and low temperature resistant modified allyl molding compound of the present invention may not contain a flame retardant or reduce the amount of the flame retardant.

[0023] The curing agent is selected from one or more of hydrogen peroxide, dibenzoyl peroxide, tert-butyl peroxy 2-ethylhexanoate, tert-butyl perbenzoate, diisopropylbenzene peroxide, di-tert-butyl peroxyisopropylbenzene and 2,3-dimethyl-2,3-diphenylbutane; further preferably, a combination of 2,3-dimethyl-2,3-diphenylbutane and hydrogen peroxide is used, which can not only enhance and toughen the material, but also reduce the amount of curing agent, and is also beneficial to improve the heat resistance of the allyl molding compound. When the curing agent contains 2,3-dimethyl-2,3-diphenylbutane, the formula of the high and low temperature resistant modified allyl molding compound of the present invention may not contain a flame retardant or reduce the amount of the flame retardant.

[0024] The demoulding agent is one or a combination of two or more selected from zinc stearate, calcium stearate, magnesium stearate, pentaerythritol stearate and palm wax.

[0025] The flame retardant is one or a combination of two or more selected from magnesium hydroxide, aluminum hydroxide, 2,3-dimethyl-2,3-diphenylbutane, zinc borate, antimony trioxide, molybdenum trioxide and tributyl phosphate.

[0026] The pigment is one or a combination of two or more selected from titanium dioxide, carbon black, permanent yellow, iron red, phthalocyanine blue, phthalocyanine green and permanent violet.

[0027] In the above technical scheme, in step a) of preparing a solid modified allyl resin, it is preferred to weigh the olefin compound having a fluorene ring, the acrylate compound having a double alicyclic ring and the solvent according to the weight percentage of 20-25%, 20-25% and the remainder. The olefin compound having a fluorene ring is preferably selected from one or a combination of two or more of 9,9-bis(4-allyloxyphenyl)fluorene, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene and 9,9-bis[4-[(4-vinylphenyl)methoxy]phenyl]fluorene, and more preferably 9,9-bis(4-allyloxyphenyl)fluorene and / or 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene. In this step, it is preferred to dissolve the olefin compound having a fluorene ring and the acrylate compound having a double alicyclic ring in the solvent at 50-60°C.

[0028] In the above technical solution, in step b) of preparing the solid modified allyl resin, the low molecular weight solid allyl resin refers to a low molecular weight solid allyl resin having a weight average molecular weight of 2×10 4 ~5×10 4 Preferably, one or a combination of two or more of diallyl phthalate resin, diallyl isophthalate resin, diallyl terephthalate resin, diallyl naphthalate resin, triallyl cyanurate resin and triallyl isocyanurate resin with a molecular weight within the above range is selected.

[0029] In the above technical scheme, in step b) of preparing the solid modified allyl resin, after placing the low molecular weight solid allyl resin in a reactor, preferably under the condition of atmosphere protection (such as nitrogen, etc.), the composite modifier, initiator and reaction are added. The reaction time after adding the initiator is usually 0.5 to 5 hours, preferably 2 to 5 hours. In this step, the initiator can be a conventional choice in the prior art, specifically, it can be selected from azobisisobutyronitrile, hydrogen peroxide, dibenzoyl peroxide and peroxy 2-ethylhexanoic acid tert-butyl ester or a combination of two or more thereof.

[0030] The method for preparing the high and low temperature resistant allyl molding compound comprises the following steps:

[0031] 1) preparing a solid modified allyl resin, comprising the following steps:

[0032] a) weighing 15-30% of an olefin compound having a fluorene ring, 15-30% of an acrylate compound having a double aliphatic ring and the remainder of a solvent by weight percentage; dissolving the olefin compound having a fluorene ring and the acrylate compound having a double aliphatic ring in the solvent to obtain a composite modifier; wherein,

[0033] The olefin compound having a fluorene ring is a compound represented by the following formula (A):

[0034]

[0035] In formula (A), R represents one or a combination of two or more of an alkylene group, a phenyl group, a carboxyl group, a carbonyl group and an ether group;

[0036] The acrylate compound having a double aliphatic ring is isobornyl acrylate and / or isobornyl methacrylate;

[0037] The solvent is one or a combination of two or more selected from ethanol, isopropanol, ether, toluene and xylene;

[0038] b) weighing 58-65% of a low molecular weight solid allyl resin, 30-40% of a composite modifier and the remainder of an initiator by weight percentage; placing the low molecular weight solid allyl resin in a reaction kettle, adding the composite modifier, stirring evenly, heating to 80-130° C., adding the initiator to react, cooling after the reaction is completed, and crushing to obtain a solid modified allyl resin;

[0039] 2) Weigh each component according to the formula, mix them evenly, and granulate them after refining and plasticizing to obtain the product.

[0040] In step 1) of the above preparation method, the preferred selection of the olefin compound having a fluorene ring and the acrylate compound having a bicyclic ring, the selection of various parameters such as the low molecular weight solid allyl resin and the initiator, etc. are the same as described above.

[0041] In step 2) of the above preparation method, the uniformly mixed material is usually placed in a co-rotating twin-screw extruder for plasticizing, and the temperature of each section of the co-rotating twin-screw extruder is usually controlled at 60-90°C, and the melt temperature is controlled at 80±10°C; the extruded material is sent to a single-screw granulator for granulation, and the temperature of each section of the single-screw granulator is usually controlled at 70-100°C to obtain regular or irregular granular plastics. The obtained granular plastics are subjected to conventional post-processing procedures such as cooling, magnetic separation, batch mixing, screening, weighing, and packaging to obtain the high and low temperature resistant allyl molding compound.

[0042] Compared with the prior art, the present invention is characterized in that:

[0043] 1. The present invention selects an olefin compound having a fluorene ring and an acrylate compound having a bicyclic aliphatic ring in a specific ratio as a composite modifier, and the double bonds of the olefinic part and the acrylate part in the structure are co-prepolymerized with a low molecular weight allyl resin through free radical polymerization, and huge non-polar biphenyl polyaromatic ring groups and bicyclic alkyl groups are introduced into the allyl resin system, which greatly increases the rigid condensed ring structure of the polymer chain and provides strong steric protection to the polymer chain. The two act synergistically, significantly reducing the thermal expansion coefficient while effectively increasing the glass transition temperature, so that the allyl molding compound prepared by the obtained solid modified allyl resin has excellent dimensional stability, high and low temperature resistance, impact resistance and wear resistance.

[0044] 2. The high and low temperature resistant allyl molding compound described in the present invention has low thermal expansion coefficient, low shrinkage rate, high glass transition temperature, impact resistance, and excellent electrical properties, flame retardant properties, water resistance, chemical resistance, wear resistance and environmental friendliness. Experimental results show that the thermal expansion coefficient of the molded parts of the high and low temperature resistant allyl molding compound described in the present invention can be as low as 26ppm / ℃ (26~37ppm / ℃), the molding shrinkage rate can be as low as 0.20% (0.20~0.30%), the glass transition temperature can be as high as 249℃ (240~249℃), and the load deformation temperature can be as high as 291℃ (282~291℃), which can be better suitable for the use requirements of high-performance electronic components in special fields such as aerospace, navigation and deep diving. DETAILED DESCRIPTION

[0045] In order to better explain the technical solution of the present invention, the present invention is further described in detail below in conjunction with embodiments, but the embodiments of the present invention are not limited thereto.

[0046] Example 1: Preparation of solid modified allyl resin

[0047] a) weighing 25 wt% of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, 25 wt% of isobornyl acrylate and 50 wt% of ethanol for later use; placing 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene in ethanol at 50° C., stirring to dissolve, then adding isobornyl acrylate, and continuing to stir to dissolve to obtain a composite modifier;

[0048] b) Weigh 60 wt% of solid diallyl phthalate resin (weight average molecular weight is about 2×10 4), 38wt% of the composite modifier prepared in step a) and 2wt% of hydrogen peroxide for standby use; solid diallyl phthalate resin was put into a reaction kettle, stirred at a speed of 60rpm, and nitrogen was passed through, the composite modifier was added dropwise, the temperature was raised to 90°C, hydrogen peroxide was added, and the reaction was kept warm for 5h. After the reaction was completed, ethanol was evaporated and removed, the resin was rapidly cooled, crushed, and sieved to obtain a solid modified allyl resin (weight average molecular weight of about 4×10 4 ).

[0049] Comparative Example 1-1

[0050] Example 1 was repeated, except that isobornyl acrylate was omitted and the amount of isobornyl acrylate was replaced by an equal amount of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, that is, step a) was performed as follows:

[0051] a) weighing 50 wt% of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene and 50 wt% of ethanol for later use; placing 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene in ethanol at 50° C., stirring and dissolving, to obtain a composite modifier.

[0052] Example 2: Preparation of solid modified allyl resin

[0053] a) weighing 25 wt% of 9,9-bis(4-allyloxyphenyl)fluorene, 25 wt% of isobornyl methacrylate and 50 wt% of ethanol for later use; placing 9,9-bis(4-allyloxyphenyl)fluorene in ethanol at 50° C., stirring to dissolve, then adding isobornyl methacrylate, and continuing to stir to dissolve, to obtain a composite modifier;

[0054] b) Weigh 60 wt% of solid diallyl isophthalate resin (weight average molecular weight is about 3×10 4 ), 38wt% of the composite modifier prepared in step a) and 2wt% of dibenzoyl oxide for standby use; solid diallyl isophthalate resin is put into a reaction kettle, stirred at a speed of 80rpm, and nitrogen is passed through, the composite modifier is added dropwise, the temperature is raised to 120°C, dibenzoyl oxide is added, and the reaction is kept warm for 2h. After the reaction is completed, ethanol is evaporated and removed, the resin is rapidly cooled, crushed, and sieved to obtain a solid modified allyl resin (weight average molecular weight is about 5×10 4 ).

[0055] Comparative Example 2-1

[0056] Example 1 was repeated, except that isobornyl methacrylate was omitted and the amount of isobornyl methacrylate was replaced by an equal amount of 9,9-bis(4-allyloxyphenyl)fluorene, that is, step a) was performed as follows:

[0057] a) Weigh 50 wt% of 9,9-bis(4-allyloxyphenyl)fluorene and 50 wt% of ethanol and set aside; place 9,9-bis(4-allyloxyphenyl)fluorene in ethanol at 50° C. and stir to dissolve to obtain a composite modifier.

[0058] Comparative Example 2-2

[0059] Example 1 was repeated, except that 9,9-bis(4-allyloxyphenyl)fluorene was omitted and the amount of the original 9,9-bis(4-allyloxyphenyl)fluorene was replaced by an equal amount of isobornyl methacrylate, that is, step a) was performed as follows:

[0060] a) weighing 50 wt% of isobornyl methacrylate and 50 wt% of ethanol for later use; placing isobornyl methacrylate in ethanol at room temperature, stirring and dissolving, to obtain a composite modifier.

[0061] Example 3: Preparation of solid modified allyl resin

[0062] a) weighing 25 wt% of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, 25 wt% of isobornyl acrylate and 50 wt% of ethanol for later use; placing 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene in ethanol at 50° C., stirring to dissolve, then adding isobornyl acrylate, and continuing to stir to dissolve to obtain a composite modifier;

[0063] b) Weigh 62 wt% of a low molecular weight solid allyl resin (with a weight average molecular weight of about 3×10 4 The solid diallyl phthalate resin has a weight average molecular weight of about 3×10 4 The solid diallyl phthalate resin is placed in a reaction kettle, stirred at a speed of 70 rpm, and protected by nitrogen, and the composite modifier is added dropwise. The temperature is raised to 100° C., tert-butyl peroxide 2-ethylhexanoate is added, and the reaction is kept warm for 4 hours. After the reaction is completed, ethanol is evaporated and removed, and the mixture is rapidly cooled, crushed, and sieved to obtain a solid modified allyl resin (weight average molecular weight is about 6×10 4 ).

[0064] Example 4: Preparation of solid modified allyl resin

[0065] a) weighing 25 wt% of 9,9-bis(4-allyloxyphenyl)fluorene, 25 wt% of isobornyl methacrylate and 50 wt% of ethanol for later use; placing 9,9-bis(4-allyloxyphenyl)fluorene in ethanol at 50° C., stirring to dissolve, then adding isobornyl methacrylate, and continuing to stir to dissolve, to obtain a composite modifier;

[0066] b) Weigh 62 wt% of a low molecular weight solid allyl resin (with a weight average molecular weight of about 3×10 4 The solid diallyl isophthalate resin has a weight average molecular weight of about 3×10 4 The solid diallyl phthalate resin was put into a reaction kettle, stirred at a speed of 70 rpm, and nitrogen was passed through, the composite modifier was added dropwise, the temperature was raised to 110° C., tert-butyl peroxide 2-ethylhexanoate was added, and the reaction was kept warm for 4 hours. After the reaction was completed, ethanol was evaporated and removed, the resin was rapidly cooled, crushed, and sieved to obtain a solid modified allyl resin (weight average molecular weight of about 6×10 4 ).

[0067] Example 5: High and low temperature resistant allyl molding compound of the present invention

[0068] (1) Formulation

[0069] 33 parts of solid modified allyl resin, prepared according to the method described in Example 1;

[0070] 26 parts of reinforcing fiber, short chopped alkali-free glass fiber;

[0071] 30 parts of filler, consisting of magnesium hydroxide and aluminum hydroxide in a weight ratio of 2:1;

[0072] 8 parts of curing agent, dicumyl peroxide;

[0073] 1.5 parts of release agent, zinc stearate;

[0074] 1.5 parts of pigment, titanium dioxide is selected.

[0075] (2) Preparation method

[0076] Weigh each component according to the above formula, put it into a high-speed mixer, mix it evenly, and then plasticize it through a twin-screw extruder. The temperature of each section of the twin-screw extruder is controlled at 60-90°C, and the melt temperature is controlled within the range of 80±10°C; the extrudate is sent to a single-screw granulator for granulation. The temperature of each section of the single-screw granulator is controlled at 70-100°C to obtain regular or irregular granular plastics. After cooling, magnetic separation, batch mixing, sieving, weighing, and packaging, the high and low temperature resistant allyl molding compound is obtained.

[0077] Comparative Example 5-1

[0078] Example 5 was repeated, except that the solid modified allyl resin in the formulation was prepared according to the method described in Comparative Example 1-1.

[0079] Comparative Example 5-2

[0080] Example 5 was repeated, except that the solid modified allyl resin in the formulation was replaced by an equal amount of solid diallyl phthalate resin (weight average molecular weight of about 2×10 4 )replace.

[0081] Example 6: High and low temperature resistant allyl molding compound of the present invention

[0082] (1) Formulation

[0083] 28 parts of solid modified allyl resin, prepared according to the method described in Example 2;

[0084] 30 parts of reinforcing fiber, short chopped alkali-free glass fiber;

[0085] 33 parts of filler, composed of calcium carbonate and zirconium tungstate in a weight ratio of 1:1;

[0086] 5 parts of curing agent, dicumyl peroxide;

[0087] 1 part of release agent, zinc stearate;

[0088] 2 parts of flame retardant, zinc borate;

[0089] 1 part of pigment, choose titanium dioxide.

[0090] (2) Preparation method

[0091] Same as Example 5.

[0092] Comparative Example 6-1

[0093] Example 6 was repeated, except that the solid modified allyl resin in the formulation was prepared according to the method described in Comparative Example 2-1.

[0094] Comparative Example 6-2

[0095] Example 6 was repeated, except that the solid modified allyl resin in the formulation was prepared according to the method described in Comparative Example 2-2.

[0096] Example 7: High and low temperature resistant allyl molding compound of the present invention

[0097] (1) Formulation

[0098] 30 parts of solid modified allyl resin, prepared according to the method described in Example 3;

[0099] 30 parts of reinforcing fiber, short chopped alkali-free glass fiber;

[0100] 32 parts of filler, consisting of magnesium hydroxide and silicon powder in a weight ratio of 1:1;

[0101] 6 parts of a curing agent, consisting of hydrogen peroxide and 2,3-dimethyl-2,3-diphenylbutane in a weight ratio of 1:1;

[0102] 1 part of release agent, zinc stearate;

[0103] 1 part of pigment, choose carbon black.

[0104] (2) Preparation method

[0105] Same as Example 5.

[0106] Example 8: High and low temperature resistant allyl molding compound of the present invention

[0107] (1) Formulation

[0108] 30 parts of solid modified allyl resin, prepared according to the method described in Example 4;

[0109] 30 parts of reinforcing fiber, short chopped alkali-free glass fiber;

[0110] 32 parts of filler, consisting of magnesium hydroxide and kaolin in a weight ratio of 1:1;

[0111] 6 parts of a curing agent, composed of dibenzoyl peroxide and 2,3-dimethyl-2,3-diphenylbutane in a weight ratio of 1:1;

[0112] 1 part of release agent, pentaerythritol stearate;

[0113] 1 part pigment, choose iron red.

[0114] (2) Preparation method

[0115] Same as Example 5.

[0116] Example 9: High and low temperature resistant allyl molding compound of the present invention

[0117] 1. Preparation of solid modified allyl resin

[0118] a) weighing 30 wt % of 9,9-bis[4-[(4-vinylphenyl)methoxy]phenyl]fluorene, 15 wt % of isobornyl acrylate and 55 wt % of toluene for later use; placing 9,9-bis[4-[(4-vinylphenyl)methoxy]phenyl]fluorene in toluene at 60° C., stirring to dissolve, then adding isobornyl acrylate, and continuing to stir to dissolve to obtain a composite modifier;

[0119] b) Weigh 58 wt% of solid diallyl terephthalate resin (weight average molecular weight is about 3×10 4 ), 40wt% of the composite modifier prepared in step a) and 2wt% of azobisisobutyronitrile for standby use; solid diallyl terephthalate resin is put into a reaction kettle, stirred at a speed of 60rpm, and nitrogen is passed through, the composite modifier is added dropwise, the temperature is raised to 130°C, azobisisobutyronitrile is added, and the reaction is kept warm for 2h. After the reaction is completed, toluene is evaporated and removed, the resin is rapidly cooled, crushed, and sieved to obtain a solid modified allyl resin (weight average molecular weight is about 5×10 4 ).

[0120] 2. High and low temperature resistant allyl molding compound

[0121] (1) Formulation

[0122] 35 parts of solid modified allyl resin, prepared according to the above step 1;

[0123] 32 parts of reinforcing fiber, basalt fiber is selected;

[0124] 24 parts of filler, magnesium hydroxide is selected;

[0125] 8 parts of curing agent, tert-butyl perbenzoate;

[0126] 0.5 part of release agent, palm wax is used;

[0127] 0.5 parts of pigment, choose permanent yellow.

[0128] (2) Preparation method

[0129] Same as Example 5.

[0130] Example 10: High and low temperature resistant allyl molding compound of the present invention

[0131] 1. Preparation of solid modified allyl resin

[0132] a) weighing 15 wt% of 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, 25 wt% of isobornyl methacrylate and 60 wt% of ether for later use; placing 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene in toluene at 35° C., stirring to dissolve, then adding isobornyl methacrylate, and continuing to stir to dissolve, to obtain a composite modifier;

[0133] b) Weigh 65 wt% of solid diallyl naphthalate resin (weight average molecular weight is about 2×10 4 ), 30wt% of the composite modifier prepared in step a) and 5wt% of hydrogen peroxide for standby use; solid diallyl naphthalate resin was put into a reaction kettle, stirred at a speed of 60rpm, and nitrogen was passed through, the composite modifier was added dropwise, the temperature was raised to 100°C, hydrogen peroxide was added, and the reaction was kept warm for 3h. After the reaction was completed, the ether was evaporated and removed, the mixture was rapidly cooled, crushed, and sieved to obtain a solid modified allyl resin (weight average molecular weight of about 4×10 4 ).

[0134] 2. High and low temperature resistant allyl molding compound

[0135] (1) Formulation

[0136] 25 parts of solid modified allyl resin, prepared according to the above step 1;

[0137] 25 parts of reinforcing fiber, needle-shaped wollastonite;

[0138] 34 parts of filler, calcium carbonate;

[0139] 10 parts of a curing agent, composed of hydrogen peroxide and di-tert-butyl peroxyisopropylbenzene in a weight ratio of 1:1;

[0140] 2 parts of release agent, zinc stearate;

[0141] 2 parts of flame retardant, antimony trioxide is selected;

[0142] 2 parts of pigment, choose phthalocyanine blue.

[0143] (2) Preparation method

[0144] Same as Example 5.

[0145] The thermal expansion coefficient, molding shrinkage, glass transition temperature, heat resistance, mechanical properties, electrical properties and flame retardancy of the molded parts made of the molding materials obtained in the above-mentioned Examples 5 to 10 and Comparative Examples 5-1, 5-2, 6-1 and 6-2 were tested according to relevant national industry standards, and the results are shown in the following Table 1.

[0146] Table 1:

[0147]

[0148] As can be seen from Table 1, compared with the use of unmodified solid allyl resin, the thermal expansion coefficient and molding shrinkage rate of the prepared allyl molding compound parts are reduced, and the glass transition temperature, heat resistance, mechanical properties, electrical properties and flame retardant properties are all enhanced by using the solid allyl resin modified by the olefin compound having a fluorene ring or the acrylate compound having a double aliphatic ring alone. In the present application, the thermal expansion coefficient and molding shrinkage rate of the prepared allyl molding compound parts are significantly reduced, and the glass transition temperature, heat resistance, mechanical properties, electrical properties and flame retardant properties are also significantly enhanced. The combination of the two has a synergistic effect.

[0149] After adopting the composite modified solid allyl resin specially prepared by the present invention, the obtained allyl molding compound parts can have low thermal expansion coefficient, low shrinkage rate, high glass transition temperature, dimensional stability, high and low temperature resistance, impact resistance, while also having excellent electrical properties, flame retardancy, water resistance, chemical resistance, wear resistance and environmental friendliness, etc., and are suitable for manufacturing high-performance electronic components in environments with frequent changes in high and low temperatures, and have broad application prospects in the fields of aerospace, navigation and deep diving.

[0150] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A high and low temperature resistant allyl molding compound, which is made of the following components in weight ratio: Solid modified allyl resin 25-35, reinforcing fiber 22-32, filler 24-34, curing agent 5-10, release agent 1-2, flame retardant 0-5, pigment 0-5; wherein, The solid modified allyl resin is prepared by the following method: a) weighing 15-30% of an olefin compound having a fluorene ring, 15-30% of an acrylate compound having a double aliphatic ring and the remainder of a solvent by weight percentage; dissolving the olefin compound having a fluorene ring and the acrylate compound having a double aliphatic ring in the solvent to obtain a composite modifier; wherein, The olefin compound having a fluorene ring is a compound represented by the following formula (A): In formula (A), R represents one or a combination of two or more of an alkylene group, a phenyl group, a carboxyl group, a carbonyl group and an ether group; The acrylate compound having a double aliphatic ring is isobornyl acrylate and / or isobornyl methacrylate; The solvent is one or a combination of two or more selected from ethanol, isopropanol, ether, toluene and xylene; b) weighing 58-65% of a low molecular weight solid allyl resin, 30-40% of a composite modifier and the remainder of an initiator by weight percentage; placing the low molecular weight solid allyl resin in a reaction kettle, adding the composite modifier, stirring evenly, heating to 80-130° C., adding the initiator to react, cooling after the reaction is completed, and crushing to obtain a solid modified allyl resin.

2. The high and low temperature resistant allyl molding compound according to claim 1, characterized in that In step a) of preparing a solid modified allyl resin, the olefin compound having a fluorene ring is one or a combination of two or more selected from 9,9-bis(4-allyloxyphenyl)fluorene, 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene and 9,9-bis[4-[(4-vinylphenyl)methoxy]phenyl]fluorene.

3. The high and low temperature resistant allyl molding compound according to claim 1, characterized in that In the step a) of preparing the solid modified allyl resin, 20-25% of an olefin compound having a fluorene ring, 20-25% of an acrylate compound having a double aliphatic ring and the rest of the solvent are weighed in weight percentage.

4. The high and low temperature resistant allyl molding compound according to claim 1, characterized in that In step b) of preparing the solid modified allyl resin, the initiator is one or a combination of two or more selected from azobisisobutyronitrile, hydrogen peroxide, dibenzoyl peroxide and tert-butyl peroxy-2-ethylhexanoate.

5. The high and low temperature resistant allyl molding compound according to any one of claims 1 to 4, characterized in that In step b) of preparing the solid modified allyl resin, after placing the low molecular weight solid allyl resin in a reaction kettle, the composite modifier and initiator are added and reacted under atmosphere protection conditions.

6. The high and low temperature resistant allyl molding compound according to any one of claims 1 to 4, characterized in that: In step b) of preparing the solid modified allyl resin, the reaction time is 0.5 to 5 hours.

7. The high and low temperature resistant allyl molding compound according to any one of claims 1 to 4, characterized in that: The weight ratio of each component is: Solid modified allyl resin 28-32, reinforcing fiber 25-30, filler 28-32, curing agent 5-8, release agent 1-1.5, flame retardant 0-2, pigment 0-2.

8. The high and low temperature resistant allyl molding compound according to any one of claims 1 to 4, characterized in that: The reinforcing fibers are inorganic fibers; The filler is one or a combination of two or more selected from magnesium hydroxide, aluminum hydroxide, zirconium tungstate, calcium carbonate, silicon powder, quartz powder, mica powder and kaolin; The curing agent is one or a combination of two or more selected from hydrogen peroxide, dibenzoyl peroxide, tert-butyl peroxy 2-ethylhexanoate, tert-butyl peroxybenzoate, diisopropylbenzene peroxide, di-tert-butyl peroxyisopropylbenzene and 2,3-dimethyl-2,3-diphenylbutane.

9. The high and low temperature resistant allyl molding compound according to claim 8, characterized in that: The inorganic fiber is one or a combination of two or more selected from short alkali-free glass fiber, basalt fiber and needle-shaped wollastonite.

10. The method for preparing the high and low temperature resistant allyl molding compound according to any one of claims 1 to 9, comprising the following steps: 1) preparing a solid modified allyl resin, comprising the following steps: a) weighing 15-30% of an olefin compound having a fluorene ring, 15-30% of an acrylate compound having a double aliphatic ring and the remainder of a solvent by weight percentage; dissolving the olefin compound having a fluorene ring and the acrylate compound having a double aliphatic ring in the solvent to obtain a composite modifier; wherein, The olefin compound having a fluorene ring is a compound represented by the following formula (A): In formula (A), R represents one or a combination of two or more of an alkylene group, a phenyl group, a carboxyl group, a carbonyl group and an ether group; The acrylate compound having a double aliphatic ring is isobornyl acrylate and / or isobornyl methacrylate; The solvent is one or a combination of two or more selected from ethanol, isopropanol, ether, toluene and xylene; b) weighing 58-65% of a low molecular weight solid allyl resin, 30-40% of a composite modifier and the remainder of an initiator by weight percentage; placing the low molecular weight solid allyl resin in a reaction kettle, adding the composite modifier, stirring evenly, heating to 80-130° C., adding the initiator to react, cooling after the reaction is completed, and crushing to obtain a solid modified allyl resin; 2) Weigh the components according to the formula of claim 1, mix them evenly, extrude them after plasticizing, and granulate them to obtain the product.

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